초록 ▼

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with th

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

대표청구항 ▼

1. A process for performing at least one of electrocatalytic hydrogenation (ECH) and electrocatalytic hydrodeoxygenation (ECHDO) of an organic substrate, the process comprising: (a) providing a reaction mixture comprising (i) water in an amount of at least 25 wt. % relative to the reaction mixture a

1. A process for performing at least one of electrocatalytic hydrogenation (ECH) and electrocatalytic hydrodeoxygenation (ECHDO) of an organic substrate, the process comprising: (a) providing a reaction mixture comprising (i) water in an amount of at least 25 wt. % relative to the reaction mixture and (ii) an organic reactant comprising one or more functional groups selected from the group consisting of carbonyl carbon-oxygen double bonds, aromatic double bonds, ethylenic carbon-carbon double bonds, acetylenic carbon-carbon triple bonds, hydroxyl carbon-oxygen single bonds, ether carbon-oxygen single bonds, and combinations thereof;(b) contacting the reaction mixture with a first electrode and a catalytic composition comprising a skeletal metal catalyst capable of catalyzing at least one of electrocatalytic hydrogenation (ECH) and electrocatalytic hydrodeoxygenation (ECHDO);(c) electrically contacting the reaction mixture with a second electrode; and(d) applying an electrical potential between the first electrode and the second electrode to provide an electrical current therebetween and through the reaction mixture, thereby performing at least one of an ECH reaction and an ECHDO reaction to reduce or deoxygenate at least one of the functional groups of the organic reactant and to form at least one of (i) an ECH reaction product thereof and (ii) an ECHDO reaction product thereof;wherein the reaction mixture has a pH value ranging from 4 to 11 when applying the electrical potential to form the reaction product,wherein the reaction mixture is free from added water-miscible organic solvents,wherein the reaction mixture comprises a plurality of the organic reactants, the plurality being selected from the group consisting of a multicomponent bio-oil, a multicomponent bio-oil fraction, a plurality of bio-oil components, a multicomponent lignin depolymerization product, a multicomponent lignin depolymerization product fraction, a plurality of lignin depolymerization product components, and combinations thereof, andwherein the organic reactant has a conversion of at least 80% as a result the at least one of the ECH reaction and the ECHDO reaction in part (d). 2. The process of claim 1, wherein the reaction mixture has an initial pH value ranging from 4 to 10 and is maintained in the range from 4 to 10 during the application of the electrical potential to form the reaction product. 3. The process of claim 1, wherein the reaction mixture further comprises a pH buffer to maintain the pH value of the reaction mixture in a selected range during the application of the electrical potential to form the reaction product. 4. The process of claim 1, wherein the metal of the skeletal metal catalyst comprises at least one of Ni and a Ni-containing alloy. 5. The process of claim 1, wherein the skeletal metal catalyst comprises an alkaline leaching product of an alloy comprising (i) aluminum and (ii) nickel as the metal of the skeletal metal catalyst. 6. The process of claim 1, wherein the skeletal metal catalyst has a microporous structure with a specific BET surface area ranging from 5 m2/g to 100 m2/g. 7. The process of claim 1, wherein the catalytic composition is immobilized on the first electrode. 8. The process of claim 7, wherein the catalyst composition comprises an alkaline leaching product of a composite material comprising (i) a metal matrix and (ii) an alloy comprising (A) aluminum and (B) the metal of the skeletal metal catalyst. 9. The process of claim 1, wherein the catalyst composition is capable of catalyzing at least one of (i) ECH of unsaturated carbon-carbon bonds in an organic substrate, (ii) ECH of carbon-oxygen double bonds in an organic substrate, and (iii) ECHDO of carbon-oxygen single bonds in an organic substrate. 10. The process of claim 1, wherein the organic reactant comprises the aromatic double bonds and at least 80% of the aromatic double bonds are hydrogenated via ECH in the ECH reaction product. 11. The process of claim 1, wherein the organic reactant comprises the ether carbon-oxygen single bonds and at least 80% of the ether carbon-oxygen single bonds are cleaved via ECHDO in the ECHDO reaction product. 12. The process of claim 1, wherein the aromatic double bonds are present and in a functional group selected from the group consisting of benzenes, phenols, furans, pyridines, pyrazines, imidazoles, pyrazoles, oxazoles, thiophenes, naphthalenes, higher fused aromatics, and combinations thereof. 13. The process of claim 1, wherein the functional group comprises an aromatic CH group, and the corresponding ECH reaction product comprises a CH2 group. 14. The process of claim 1, wherein the functional group comprises an ether R1—O—R2 group, and the corresponding ECH or ECHDO reaction products comprise one or more of a R1H, R2OH, R1OH, and R2H, where R1 and R2 are substituents containing from 1 to 10 carbon atoms. 15. The process of claim 1, wherein: (i) the functional group comprises an ether R1—O—R2 group,(ii) the corresponding ECH or ECHDO reaction products comprise one or more of a R1H, R2OH, R1OH, and R2H,(iii) R1 is a substituted or unsubstituted aromatic or heteroaromatic substituent containing 3 to 20 carbon atoms, and(iv) R2 is a substituted or unsubstituted alkyl substituent containing from 1 to 10 carbon atoms. 16. The process of claim 1, wherein: (i) the functional group comprises an ether R1—O—R2 group,(ii) the corresponding ECH or ECHDO reaction products comprise one or more of R1*H and R2OH,(iii) R1 is a substituted or unsubstituted aromatic or heteroaromatic substituent containing 3 to 20 carbon atoms,(iv) R1* is a hydrogenated analog of R1, and(v) R2 is a substituted or unsubstituted alkyl substituent containing from 1 to 10 carbon atoms. 17. The process of claim 1, wherein the reaction mixture comprises a plurality of the organic reactants, the plurality being selected from the group consisting of a multicomponent bio-oil, a multicomponent bio-oil fraction, a plurality of bio-oil components, and combinations thereof. 18. The process of claim 1, wherein the reaction mixture comprises a plurality of the organic reactants, the plurality being selected from the group consisting of a multicomponent lignin depolymerization product, a multicomponent lignin depolymerization product fraction, a plurality of lignin depolymerization product components, and combinations thereof. 19. The process of claim 1, further comprising: (e) recovering or separating the reaction product from the reaction mixture. 20. The process of claim 1, comprising performing the ECH or ECHDO reaction at a temperature ranging from 0° C. to 100° C. and at a pressure ranging from 0.8 atm to 1.2 atm. 21. The process of claim 1, wherein the reaction mixture further comprises a surfactant. 22. The process of claim 1, wherein the second electrode comprises cobalt(III) phosphate. 23. A process for performing at least one of electrocatalytic hydrogenation (ECH) and electrocatalytic hydrodeoxygenation (ECHDO) of an organic substrate, the process comprising: (a) providing a reaction mixture comprising (i) water in an amount of at least 15 wt. % relative to the reaction mixture and (ii) a plurality of organic reactants, wherein: the plurality of organic reactants is selected from the group consisting of a multicomponent bio-oil, a multicomponent bio-oil fraction, a plurality of bio-oil components, and combinations thereof,the organic reactants collectively comprise one or more functional groups selected from the group consisting of carbonyl carbon-oxygen double bonds, aromatic double bonds, ethylenic carbon-carbon double bonds, acetylenic carbon-carbon triple bonds, hydroxyl carbon-oxygen single bonds, ether carbon-oxygen single bonds, and combinations thereof; andthe reaction mixture is free from added water-miscible organic solvents;(b) contacting the reaction mixture with a first electrode and a catalytic composition comprising a skeletal metal catalyst capable of catalyzing at least one of electrocatalytic hydrogenation (ECH) and electrocatalytic hydrodeoxygenation (ECHDO);(c) electrically contacting the reaction mixture with a second electrode; and(d) applying an electrical potential between the first electrode and the second electrode to provide an electrical current therebetween and through the reaction mixture, thereby performing at least one of an ECH reaction and an ECHDO reaction to reduce or deoxygenate at least one of the functional groups of the organic reactants and to form at least one of (i) an ECH reaction product thereof and (ii) an ECHDO reaction product thereof, wherein the organic reactants have a conversion of at least 80% as a result the at least one of the ECH reaction and the ECHDO reaction. 24. The process of claim 23, wherein the bio-oil is a reaction product produced from fast pyrolysis of biomass. 25. The process of claim 23, wherein the water is present in the reaction mixture in an amount of at least 25 wt. % relative to the reaction mixture. 26. The process of claim 23, wherein the reaction mixture comprises the multicomponent bio-oil fraction, the fraction having been obtained by extraction of bio-oil using a solvent comprising one or more of water, diethyl ether, ethyl acetate, dichloromethane, chloroform, toluene, and hexane. 27. The process of claim 23, wherein the reaction mixture comprises a plurality of bio-oil pyrolysis products selected from the group consisting of acetol, hydroxyacetaldehyde, glyoxal, formaldehyde, acetic acid, phenol, guaiacol, syringol, levoglucosan, furfural, glucose, xylose, substituted derivatives thereof, and combinations thereof. 28. The process of claim 23, wherein the reaction product comprises one or more of ethylene glycol, propylene glycol, cyclohexanol, furfuryl alcohol, and methanol. 29. The process of claim 23, wherein the pH value of the reaction mixture ranges from 6 to 9. 30. The process of claim 23, wherein the reaction mixture further comprises a pH buffer to maintain the pH value of the reaction mixture in a selected range during the application of the electrical potential to form the reaction product.